Assembly of Seven Supramolecular Compounds with p-Sulfonatocalix[6]arene

Seven supramolecular compounds comprising p-sulfonatocalix[6]arene and transition metals, {[Cu(Imz)-(phen)(H2O)](4)[C6AS]}center dot 10H(2)O (1), {[Cu(Imz)(2)(phen)](2)[Cu(Imz)(phen)(H2O)(2)](2)[C6AS]}center dot 13.3H(2)O (2), {[M(phen)(2)(H2O)]-[(M(phen)(2)](2)[C6AS]}center dot nH(2)O (3 and 4) (3: M = Co and n = 29.6; 4: M = Zn and n = 29.9), {[Cu(phen)(2)](4)[C6AS]}(2)center dot 13H(2)O (5), [H3O](2)[Co(phen)(3)](2)[C6AS]center dot 10.7H(2)O(6), and [Cu(phen)(2)(H2O)](2){[Cu(phen)(2)](2)[C6AS]}center dot 8H(2)O(7)(phen = 1,10-phenanthroline, C6AS = p-sulfonatocalix[6]arene, Imz = imidazole), have been synthesized by a hydrothermal method and structurally characterized by IR spectroscopy, thermogravimetric-differential thermal analysis (TG-DTA), and single crystal X-ray diffraction.

Self-Assembly from Two-Dimensional Layered Networks to Tetranuclear Structures: Syntheses, Structures, and Properties of Four Copper-Thiacalix[4]arene Compounds

Two new copper-thiacalix[4]arene compounds, [Cu-2(1)-Cl-2(H(4)TC4A)](CH3OH) (1) and [Cu(I)2Cl(2)(H(4)PTC4A)](CH3OH)(CHCl3)(0.5) (2) (where H(4)TC4A = p-tert-butylthiacalix[4]arene and H(4)PTC4A = p-phenylthiacalix[4]arene), were synthesized by the solvothermal method in the mixed CH3OH/CHCl3 (1: 1) solvent and reassembled in air at room temperature to two other structures, [(Cu4Cl3)-Cl-II(HCO2)(TC4A)(CH3-OH)(2)(H2O)](CHCl3)(CH3OH)(2.7) (3) and [(Cu4Cl4)-Cl-II(PTC4A)(CH3OH)(4)] (4), respectively. All these four compounds were characterized by TG analyses, FTIR spectroscopy, and singlecrystal X-ray diffraction analyses. Compounds 1 and 2 feature two-dimensional layered networks, while compounds 3 and 4 are assembled by some tetranuclear units.

Starburst substituted hexaazatriphenylene compounds: synthesis, photophysical and electrochemical properties

Starburst-substituted hexaazatriphenylene Compounds have been designed and synthesized by introducing various peripheral aryl substituents to the central heterocyclic core. The effects of various substituent groups on the photophysical and electrochemical properties of the substituted hexaazatriphenylene have been investigated. Significant red-shifts of the absorption peak (from 413 nm to 530 nm) and emission peak (from 432 nm to 700 nm) were observed when the electron-donating ability of the aryl substituents was increased, corresponding to a decrease in the band gap from 2.90 eV to 2.05 eV. Introducing bulky substituents with weak electron-donating ability enhances the fluorescence quantum yield from 23% to 87%. In contrast, incorporating aryl substituents with strong electron-donating ability decreases the fluorescence quantum yield.

Synthesis and Characterization of One-Dimensional and Molecular M(tren)InAsS4 (M = Mn, Co, and Zn) Compounds with a Noncondensed AsS33- Unit

Four transition-metal-amine complexes incorporating indium thioarsenates with the general formula M(tren)InAsS4 (M=Mn, Co, and Zn) and a noncondensed AsS33- unit have been prepared and characterized. Single-crystal X-ray diffraction analyses show that compound 1 (M=Mn) crystallizes in the triclinic crystal system (space group: P (1) over bar) and consists of a one-dimensional (1D) inorganic (1)(infinity){[InAsS4](2-)} chain and [Mn(tren)](2+) groups bonded to the opposite sides of an eight-membered In2As2S4 ring along the backbone of the infinite inorganic chains. Compounds 2 (M=Mn), 3 (M=Zn), and 4 (M=Co) are isomorphous molecular compounds. They all crystallize in the monoclinic crystal system (space group: P2(1)/c). The Mn2+ cation of [Mn(tren)](2+) in 1 has a distorted octahedral environment, while the transition-metal cations of [M(tren)](2+) in the other three compounds locate in trigonal-bipyramidal environments.

Poly[[(pentaethylenehexamine)manganese(II)] [hepta-mu-selenido-tritin(IV)]]: a tin-selenium net with remarkable flexibility

The title compound, {[Mn(C10H28N6)][Sn3Se7]}(n), consists of anionic (infinity){[Sn3Se7](2-)} layers interspersed by [Mn(peha)](2+) complex cations ( peha is pentaethylenehexamine). Pseudo-cubic (Sn3Se4) cluster units within each layer are held together to form a 6(3) net with a hole size of 8.74 x 13.87 angstrom. Weak N-H center dot center dot center dot Se interactions between the host inorganic frameworks and metal complexes extend the components into a three-dimensional network. The incorporation of metal complexes into the flexible anion layer dictates the distortion of the holes.

Synthesis and Spectrum of Novel Pyrazoline Fluorescent Compounds

Pyrazoline derivatives have been used widely in dyeing industry as fluorescent whitening agents due to their excellent capability. According to Schellhammer theory of the relation between chemical structure and fluorescent quality, six new fluorescent compounds were designed and synthesized which contained the benzothiazole group in the I-pyrazoline, the indole group in the 3-pyrazoline and the derivatives of phenyl in the 5-pyrazoline. The structure of target compounds was confirmed by IR, H-1 NMR, MS and elementary analysis. The fluorescence spectra showed that these compounds had good fluorescence. They could absorb ultraviolet light at near 353 nm. The fluorescence maximum emission wavelengths were about 430-443 nm. It was a kind of promising fluorescence compounds. The largest fluorescence emission wavelength and the fluorescence intensity were related to the substituted group of the compounds. When the 6-Br group was introduced into benzothiazole, the fluorescence emission wavelength exhibited a blue shift, and the fluorescence intensity increased.

Luminescent Boron-Contained Ladder-Type pi-Conjugated Compounds

Four diboron-contained ladder-type pi-conjugated compounds 1-4 were designed and synthesized. Their thermal, photophysical, electrochemical properties, as well as density functional theory calculations, were fully investigated. The single crystals of compounds 1 and 3 were grown, and their crystal structures were determined by X-ray diffraction analysis. Both compounds have a ladder-type g-conjugated framework. Compounds I and 2 possess high thermal stabilities, moderate solid-state fluorescence quantum yields, as well as stable redox properties, indicating that they are possible candidates for emitters and charge-transporting materials in electroluminescent (EL) devices. The double-layer device with the configuration of [ITO/NPB (40 nm)/1 or 2 (70 nm)/LiF (0.5 nm)/Al (200 nm)] exhibited good EL performance with the maximum brightness exceeding 8000 cd/m(2).

Antioxidant Sensors Based on Iron Diethylenetriaminepentaacetic Acid, Hematin, and Hemoglobin Modified TiO2 Nanoparticle Printed Electrodes

Antioxidant amperometric sensors based on iron-containing complexes and protein modified electrodes were developed. Indium tin oxide glass was printed with TiO2 nanoparticles, onto which iron-containing compounds and protein were adsorbed. When applied with negative potentials, the dissolved oxygen is reduced to H2O2 at the electrode surface, and the H2O2 generated in situ oxidizes Fe-II to Fe-III, and then electrochemical reduction of Fe-III therefore gives rise to a catalytic current. In the presence of antioxidants, H2O2 was scavenged, the catalytic current was reduced, and the decreased current signal was proportional to the quantity of existing antioxidants. A kinetic model was proposed to quantify the H2O2 scavenging capacities of the antioxidants. With the use of the sensor developed here, antioxidant measurements can be done quite simply: put the sensor into the sample solutions (in aerobic atmosphere), perform a cathodic polarization scan, and then read the antioxidant activity values. The present work can be complementary to the previous studies of antioxidant sensor techniques based on OH radicals and superoxide ions scavenging methods, but the sensor developed here is much easier to fabricate and use.

Structure and magnetic properties of new compounds CdYFeWO7

The solid solutions of CdYFeWO7, which are cubic pyrochlores of the type A(2)B(2)O(7), have been prepared and their structures were determined using Ab initio method. Rietveld refinement of the powder XRD data showed that CdYFeWO7 adopted cubic (Fd-3m) structure, while oxides crystallized in a defect-pyrochlore structure where both O (48f) and O'(8b) sites were partially occupied, and the frustrated cations sublattice precluded long range ordering of Fe/W in the pyrochlore structure. Charge distribution analysis also suggested incomplete occupation of different oxygen sites, thus the compound was non-stoichiometric, with the formula CdYFeW0.982O6.94, Magnetic measurements were carried out to find that Fe ions were in the high spin trivalent state. Curie Weiss paramagnetism down to similar to 5 K and the characteristic superposition between FC and ZFC suggested spin liquid rather than spin glass state.

Electrochemiluminescence-based DNA detection using guanine oxidation at electrostatic self-assembly of Ru(bpy)(3)(2+)-doped silica nanoparticles on indium tin oxide electrode

A Ru(bpy)(3)(2+)-doped silica nanoparticle-[Ru@Silica] modified indium tin oxide electrode was prepared by simple electrostatic self-assembly technique, and one-electron catalytic oxidation of guanine bases in double-strand and denatured DNA was realized using the electrochemiluminescence detection means.

Tris(2,2 '-bipyridyl) ruthenium(II) doped silica film modified indium tin oxide electrode and its electrochemiluminescent properties

An approach was reported to synthesize silica hybridized ruthenium bipyridyl complex through amidation reaction by covalent attachment of bis(bipyridyl)-4,4'-dicarboxy-2,2'-bipyridyl-ruthenium to (3-aminopropyl)-triethoxysilane. The hybrid complex then was gelatinized through acid catalytic hydrolysis method and a sol-gel modified indium, tin oxide electrode was prepared via spin coating technique. As prepared indium tin oxide electrode possesses good stability therein with excellent electrochemiluminescence behavior.

Sensitive biomimetic sensor based on molecular imprinting at functionalized indium tin oxide electrodes

We initially report an electrochemical sensing platform based on molecularly imprinted polymers (MIPs) at functionalized Indium Tin Oxide Electrodes (ITO). In this research, aminopropyl-derivatized organosilane aminopropyltriethoxysilane (APTES), which plays the role of functional monomers for template recognition, was firstly self-assembled on an ITO electrode and then dopamine-imprinted sol was spin-coated on the modified surface. APTES which can interact with template dopamine (DA) through hydrogen bonds brought more binding sites located closely to the surface of the ITO electrode, thus made the prepared sensor more sensitive for DA detection. Potential scanning is presented to extract DA from the modified film, thus DA can rapidly and completely leach out. The affinity and selectivity of the resulting biomimetic sensor were characterized using cyclic voltammetry (CV). It exhibited an increased affinity for DA over that of structurally related molecules, the anodic current for DA oxidation depended on the concentration of DA in the linear range from 2 x 10(-6) M to 0.8 x 10(-3) M with a correlation coefficient of 0.9927.In contrast, DA-templated film prepared under identical conditions on a bare ITO showed obviously lower response toward dopamine in solution.

Nanotubes of mixed-valence, transition metal compounds synthesized by solution phase approach

A solution-phase approach to synthesize four kinds of mixed-valence, transition metal compounds nanotube is described. The approach is based on the self-assembly of siloxane sol. The resulted production of mixed-valence, transition metal compounds share a common structural characteristic of tubular geometrical morphology, at least for the ones we studied. The results demonstrate that the synthesis strategy can be a general route for preparation of compound nanotubes. In addition, the size control of nanotubular materials can be easily achieved through varying the ionic strength of solution. Based on the strategy, the diameters of ultrathin Ru-Fe nanotubes can be easily tuned between 100 nm and 800 nm.

Investigation on relationship between charge transfer position and dielectric definition of average energy gap in Eu3+-doped compounds

The dielectric definition of average energy gap E-g of the chemical bond has been calculated quantitatively in Eu3+-doped 30 lanthanide compounds based on the dielectric theory of chemical bond for complex structure crystals. The relationship between the experimental charge transfer (CT) energy of Eu3+ and the corresponding average energy gap E-g has been studied. The results show that the CT energy increases linearly with increasing of the average energy gap E-g. The linear model is obtained. It allows us to predict the CT position of Eu3+-doped lanthanide compounds with knowledge of the crystal structure and index of refraction. Applied to the Ca4GdO(BO3)(3):Eu and Li2Lu5O4(BO3)(3):Eu crystals, the predicted results of CT energies are in good agreement with the experimental values, and it can be concluded that the lowest CT energy in Li2Lu5O4(BO3)(3):Eu originates from the site of Lu1.